3-methoxyanilinium 3-carboxy-4-hydroxybenzenesulfonate dihydrate.

Transcription

1 3-methoxyanilinium 3-carboxy-4-hydroxybenzenesulfonate dihydrate. Author Smith, Graham, D. Wermuth, Urs, Healy, Peter Published 2006 Journal Title Acta crystallographica. Section E, Structure reports online DOI Copyright Statement The Author(s) For information about this journal please refer to the journal's website. All articles published in Acta Crystallographica Section E are open access and distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. See creativecommons.org/licenses/by/2.0/uk/legalcode Downloaded from Link to published version Griffith Research Online

2 Acta Crystallographica Section E Structure Reports Online ISSN Editors: W. Clegg and D. G. Watson 3-Methoxyanilinium 3-carboxy-4-hydroxybenzenesulfonate dihydrate Graham Smith, Urs D. Wermuth and Peter C. Healy Copyright International Union of Crystallography Author(s) of this paper may load this reprint on their own web site provided that this cover page is retained. Republication of this article or its storage in electronic databases or the like is not permitted without prior permission in writing from the IUCr. Acta Cryst. (2006). E62, o2313 o2315 Smith et al. ffl C 7H 10 NO + C 7 H 5 O 6 S 2H 2 O

3 Acta Crystallographica Section E Structure Reports Online ISSN Methoxyanilinium 3-carboxy-4-hydroxybenzenesulfonate dihydrate Graham Smith, a * Urs D. Wermuth a and Peter C. Healy b a School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and b School of Science, Griffith University, Nathan, Queensland 4111, Australia The 1:1 proton-transfer compound of m-anisidine with 5- sulfosalicylic acid, 3-methoxyanilinium 3-carboxy-4-hydroxybenzenesulfonate dihydrate, C 7 H 10 NO + C 7 H 5 O 6 S 2H 2 O, is a three-dimensional framework structure built from hydrogenbonding interactions involving the aminium group of the cation, the two water molecules of solvation and the sulfonate, carboxylate and phenolic substituent groups of the anion. Received 8 May 2006 Accepted 9 May 2006 Correspondence g.smith@qut.edu.au Key indicators Single-crystal X-ray study T = 297 K Mean (C C) = Å R factor = wr factor = Data-to-parameter ratio = 8.6 For details of how these key indicators were automatically derived from the article, see Comment A number of 1:1 proton-transfer compounds of 3-carboxy-4- hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) with aniline-type Lewis bases have been reported: with aniline (Bakasova et al., 1991), the 4-X-substituted anilines (X =F,Cl, Br) (Smith et al., 2005a), X =CO 2 H (Smith et al., 2005b), 3- aminobenzoic acid (Smith, 2005), and 1,4-phenylenediamine (Smith et al., 2005). In the majority of these structures, 1:1 proton-transfer compounds are formed and are usually hydrates. The structure of the compound formed from the reaction of 5-SSA with 3-methoxyaniline (m-anisidine, MANIS) in 50% ethanol water, viz. 3-methoxyanilinium 5- sulfosalicylate dihydrate, (I), reported here, also shows this common trend. # 2006 International Union of Crystallography All rights reserved In (I), the MANIS cation, the 5-SSA anion and the two water molecules of solvation (Fig. 1) form a three-dimensional hydrogen-bonded framework structure (Fig. 2). The cation and anion pairs in the asymmetric unit have assembled with their benzene rings essentially parallel [ring centroid separation (CgCg) = (3) Å and inter-plane dihedral angle, = 4.9 (5) ], and their associative functional groups lying essentially parallel to the 2 1 screw axis of the unit cell. The two water molecules of solvation (O1W and O2W) lie in layers between these end groups and serve as donors for hydrogenbonding associations with O-atom acceptors from three separate sulfonate groups, as well as one from a phenol group (Table 1). The water molecules also act as acceptors for an aminium H atom and the carboxylic acid H atom. The other aminium protons are also associated with either sulfonate O- atom acceptors or the carboxyl O-atom acceptor of the anion species, giving a three-dimensional framework structure. Acta Cryst. (2006). E62, o2313 o2315 doi: /s Smith et al. C 7 H 10 NO + C 7 H 5 O 6 S 2H 2 O o2313

4 acid) and 3-methoxyaniline (m-anisidine) in 50% ethanol water (50 ml) for 10 min under reflux. After concentration to ca 30 ml, total room-temperature evaporation of the hot-filtered solution gave palebrown prisms of (I). Figure 1 The asymmetric unit of (I). Displacement ellipsoids are drawn at the 40% probability level. The intramolecular hydrogen bond is shown as a dashed line. Crystal data C 7 H 10 NO + C 7 H 5 O 6 S 2H 2 O M r = Orthorhombic, Pna2 1 a = (6) Å b = (12) Å c = (12) Å V = (2) Å 3 Data collection Rigaku AFC-7R diffractometer! 2 scans Absorption correction: scan (TEXSAN for Windows; Molecular Structure Corporation, 1999) T min = 0.899, T max = measured reflections Refinement Refinement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 226 parameters H atoms treated by a mixture of independent and constrained refinement Z =4 D x = Mg m 3 Mo K radiation =0.25mm 1 T = 297 (2) K Prism, pale brown mm 1943 independent reflections 1462 reflections with I > 2(I) R int = max = standard reflections frequency: 150 min intensity decay: 0.9% w = 1/[ 2 (F o 2 ) + (0.1P) P] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.28 e Å 3 min = 0.35 e Å 3 Absolute structure: Flack (1983) Flack parameter: 0.13 (14) Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA Figure 2 A perspective view of the packing of (I) in the unit cell, showing hydrogen-bonding associations as dashed lines. For symmetry codes see Table 1. The 5-SSA anions have the usual intramolecular O H(phenol)O(carboxyl) hydrogen bond [2.593 (5) Å] with the carboxylic acid group lying essentially in the plane of the benzene ring [torsion angle C2 C1 C7 O71 = (5) ]. The methoxy group of the MANIS cation is also essentially coplanar with the benzene ring [torsion angle C21 C31 O31 C32 = (5) ]. Experimental The title compound, (I), was synthesized by heating 1 mmol quantities of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic O2 H2O (7) 1.88 (7) (5) 153 (8) O71 H71O2W i 0.86 (6) 1.84 (6) (7) 157 (6) N11 H11AO (7) 2.09 (8) (6) 166 (7) N11 H11AO72 ii 0.84 (7) 2.52 (8) (5) 100 (6) N11 H11BO1W iii 0.86 (8) 1.95 (8) (7) 170 (5) N11 H11CO53 iv 0.92 (8) 2.02 (8) (6) 178 (10) O1W H11WO (9) 2.12 (9) (7) 174 (9) O1W H12WO52 v 0.87 (9) 1.98 (9) (6) 161 (7) O2W H21WO53 vi 0.90 (8) 1.90 (8) (7) 180 (10) O2W H22WO51 vii 0.86 (9) 2.08 (8) (6) 161 (7) Symmetry codes: (i) x 1 2 ; y þ 1 2 ; z; (ii) x þ 1; y; z 1 2 ; (iii) x þ 3 2 ; y 1 2 ; z 1 2 ;(iv) x þ 1; y; z; (v) x þ 1; y; z þ 1 2 ; (vi) x þ 1 2 ; y þ 1 2 ; z þ 1 2 ; (vii) x þ 1; y þ 1; z þ 1 2. H atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinement in calculated positions (C H = 0.95 Å), using a riding-model approximation, with U iso (H) values fixed at 1.2U eq (C). The absolute structure was determined without any Friedel pairs. Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON. o2314 Smith et al. C 7 H 10 NO + C 7 H 5 O 6 S 2H 2 O Acta Cryst. (2006). E62, o2313 o2315

5 The School of Science, Griffith University and the School of Physical and Chemical Sciences, Queensland University of Technology are thanked for financial assistance. References Altomare, A., Burla, M. C., Camalli, M., Cascarno, C., Giacovazzo, A., Guagliardi, A. & Polidori, G. (1994). J. Appl. Cryst. 27, 435. Bakasova, Z. B., Abdybaliev, D. A., Sharipov, Kh. T., Akbaev, A. A., Ibragimov, B. T., Talipov, S. A. & Ismankulov, A. I. (1991). Uzb. Khim. Zh. pp Flack, H. D. (1983). Acta Cryst. A39, Molecular Structure Corporation (1999). MSC/AFC Diffractometer Control Software and TEXSAN for Windows (Version 1.06). MSC, 9009 New Trails Drive, The Woodlands, TX , USA. Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Smith, G. (2005). Acta Cryst. E61, o3398 o3400. Smith, G., Wermuth, U. D. & Healy, P. C. (2005). Acta Cryst. C61, o555 o558. Smith, G., Wermuth, U. D. & White, J. M. (2005a). Acta Cryst. C61, o105 o109. Smith, G., Wermuth, U. D. & White, J. M. (2005b). Acta Cryst. E61, o313 o316. Spek, A. L. (2003). J. Appl. Cryst. 36, Acta Cryst. (2006). E62, o2313 o2315 Smith et al. C 7 H 10 NO + C 7 H 5 O 6 S 2H 2 O o2315